Specific substituted iminopyrrolidines



United States Patent Ofifice 3,132,151 Patented May 5, 1964 3,132,151 SPECIFIC SUBSTITUTED IMINOPOLEINES Newman M. Bortnick, Oreland, and Marian F. Fegley, Philadelphia, Pa., assign'ors to Rohm & Haas Company, Philadelphia, Pa a corporation of Delaware No Drawing. Filed May 15, 1961, Ser. No. 109,844

19 Claims. (Cl. 260313) This invention deals With specific substituted iminopyrrolidines as new compositions of matter. It also deals with a method for the preparation of these specific substituted iminopyrrolidines.

The compounds of this invention may be represented by the formula R2 4 in; =NR X cyclic ring containing 5 to 6 carbon atoms which in turn may have alkyl substituents containing a total of no more than 4 additional carbon atoms. In addition, R and R taken together with the carbon atoms to which they arejoined may form a carbocyclic ring containing 5 to 6 carbon atoms Which in turn may have alkyl substituents containing a total of no more than four additional'carbon atoms. In addition, R and R taken together With the carbon atoms to which they are joined may form a carbocyclic ring containing 5 to 6 carbon atoms which in turn may have alkyl substituents COH-\ taining a total of no more than 4 additional carbon atoms. The total number of carbon atoms in the cyanoketone should not exceed '24. The preferred embodiments are those in which R and R are alkyl groups, R is a hydrogen atom, and R is a methylgroup. R R and R may typically individually represent methyl, butyl, octyl, benzyl, phenylbutyl, cyclopentyl, cyclohexyl, phenyl, naphthyl, butylphenyl groups, and the like.

' Each of the symbols R and R represents a hydrogen atom, an alkyl group of 1 to 18 carbon atoms, an alkenyl group of 3 to 18 carbon atoms, an aryl group of up to 10 carbon atoms, an aralkyl group of up to 18 carbon atoms, an alkarylalkyl group of up to 30 carbon atoms, an alkoX- yalkyl group of 3 to 24 carbon atoms, a hydroxyalk yl group of 2 to 12 carbon atoms, and an alkylarninoalkyl group of 3 to 18 carbon atoms provided that the amino group is a secondary or tertiary structure, that is non-' primary. AlkyL- in the above definition, is tobe construed to include cycloalkyl and alkylcycloalkyl within the range of'carbon atoms previously set forth. It is preferred that R and R represent the same groups Within any single product. Typical R and R representations are hydrogen, methyl, ethyl, butyl octyl, decyl, dodecyl, octadecyl, cyclopentyl, cyclohexyl, butylcyclohexyl, octylcyclohexyl, butylcyclohexylethyl, propenyl, butenyl, hexenyl, octenyl, decenyl, dodecenyl, octadecenyl, phenyl, naphthyl, benzyl, phenylethyl, phenylbutyl, phenyldodecyl, metihylp hen yl, ethylphenyl, butylphenyl, octylphenyl, nonylphenyl, decylphenyl, hexadecylphenyl, octadecylphenyl, methylbenzyl, ethylbenzyl, butylbenzyl, octylbenzyl, dodecyl- 2 benzyl, butylphenylbutyl, octylphenylethyl, dioctylphenylethyl, dodecylphenyloctyl, methoxyethyl, methoxypropyl, methoxyhexyl, methoxydecyl, methoxyoctadecyl, ethoxyethyl, ethoxybutyl, ethoxyoctyl, ethoxydodecyl, propoxyethyl, propoxybutyl, propoxyheptyl, propoxytetradecyl, butoxyethyl, butoxybutyl, butoxyoctyl, butoxydodecyl, butoxyoctadecyl, pentoxyethyl, pentoxybutyl, pentoxydecyl, hexoxyethyl, hexoxyhexyl, hexoxydodecyl, hexoxyoctadecyl, heptoxyethyl, heptoxyoctyl, octoxyethyl, octoxybutyl, octoxyoctyl, octoxydodecyl, nonoxyf propyl, nonoxyheptyl, nonoxytridecyl, decoxyethyl, de-

coxyoctyl, undecoxybutyl, dodecoxypropyl, dodecoxydecyl, dodecoxydodecyl, tride'coxyethyl, tetradecoxypropyl, pentadecoxypentyl, hexadecoxybutyl, heptadecoxyethyl, octadecoxyethyl, octadecoxyhexyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, hydroxyoctyl, hydroxydecyl, hydroxydodecyl, ethylaminoethyl,

propylaminoethyl, butylaminopropyl, octylaminohexyl, hexylaminooctyl, heptylaminopentyl, octylaminooctyl, nonylaminoethyl, ethylaminononyl, decylaminopropyl,

propylarninododecyl, dodecylaminoethyl, dodecylaminobutyl, dodecylaminohexyl, N-methyl-N-ethylaminoethyl,

N-propyl-N-ethylaminoethyl, N-butyl-N-pentylaminoethyl, N-octyl-N-hexylaminobutyl, and N-decyl-N-butylaminobutyl.

The symbol X represents a cyano gr up, an aminornethyl group, an R NH group, or an R' A group, in which R represents a hydrogen atom, an alkyl group of 1 to 18 carbon atoms, an alkenyl group of 3 to 18 carbon atoms, an aralkyl group of up to 18 carbon atoms, an alkarylalkyl group of up to 30 carbon atoms, an alkoxyalkyl group of 3 to 24 carbon atoms, a hydroxyalkyl group of 2 to 12 carbon atoms, and an alkylaminoalkyl group of 3 to 18 carbon atoms provided that the amino group is a secondary or tertiary structure, that is nonprimary. Alkyl, in the above definition, is to be construed to include cycloalkyl and alkylcycloalkyl within the range of carbon atoms previously set forth.

Typical R representations are hydrogen, methyl, ethyl, butyl, octyl, decyl, dodecyl, octadecyl, cyclopentyl, cyclohexyl, butylcyclohexyl, octylcyclohexyl, butylcyclohexylethyl propenyl, butenyl, hexenyl, octenyl, decenyl, dodecenyl, octadecenyl, benzyl, phenylethyl, phenylbutyl, phenyldodecyl, methylbenzyl, ethylbenzyl, butylbenzyl, octylbenzyl, dodecylbenzyl, butylphenylbutyl, octylphenylethyl, dioctylphenylethyl, dodecylphenyloctyl, methoxyethyl, methoxypropyl, methoxyhexyl, methoxydecyl, methoxyoctadecyl, ethoxyethyl, ethoxybutyl, ethoxyoctyl, ethoxydodecyl, propoxyethyl, propoxybutyl, propoxyheptyl, propoxytetradecyl, butoxyethyl, butoxybutyl, butoxyoctyl, butoxydodecyl, butoxyoctadecyl, pentoxyethyl, pentoxybutyl, pentoxydecyl, hexoxyethyl, hexoxyhexyl, hexoxydodecyl, hexoxyoctadecyl, heptoxyethyl, heptoxyoctyl, octoxyethyl, octoxybutyl, octoxyoctyl, octoxydodecyl, nonoxypropyl, nonoxyheptyl, nonoxytridecyl, decoxyethyl, decoxyoctyl, undecoxybutyl, dodecoxypropyl, dodecoxydecyl, dodecoxydodecyl, tridecoxyethyl, tetradecoxypyropyl, pentadecoxypentyl, hexadecoxybutyl, heptadecoxyethyl, octadecoxyethyl, octadecoxyhexyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, hydroxyoctyl, hydroxydecyl, hy-

,clude all of the tautomeric forms.

to 12 carbon atoms, an aryl group of up to carbon atoms, an aralkyl group of up to 12 carbon atoms, an alkarylalkyl group of up to 12 carbon atoms, an alkoxyalkyl group of 3 to 12 carbon atoms, a hydroxyalkyl group of up to 12 carbon atoms, an alkylaminoalkyl group of 3 to 18 carbon atoms, provided thatthe amino group is a secondary or tertiary structure, that is nonprimary. Alkyl, in the above definition is to be construed to include cycloalkyl and alkylcycloallryl within the range of carbon atoms previously set forth.

The symbol A represents a chalcogen having an atomic weight of 16 to 32, that is, oxygen or sulfur.

The compounds of the present invention are made by reacting the compound having the formula (B) m R3 I ent invention wherein R is alkyl by employing the tautomer of B having the formula 'in place of the aforementioned imin-opyrroline reactant.

R is hydrogen or alkyl of 1 to 9 carbon atoms.

With respect to the aforementioned irninopyrroline re- Z-laurylimino-Sfi -pent amethy1ene-2,3,4,S,6,7-hexahydroactant, when R equals hydrogen, the compound repre-- sented by the formula B is to varying degrees, according principally to reaction conditions and the values of R, R R R and R in tautomeric relationship With the compounds having the following structure-s:

v (D) R2 m R i I -NHR and - (E) R? R R1 =NR It is highly probable, based on the best experimental and analytical evidence, that the predominant. tautomeric product is that of Formula E, but appreciable amounts of B and D are undoubtedly present.

In the present sense, Formula B will be referred to as the principal form of the possible tautomeric structures (B, C, D, and E), but such a reference is meant to in- Formulas B and C represent the predominant tautomeric forms when R is alkyl.

Typical reactants having the formulas B or C include 5-laurylimino-2-methyl-l-pyrroline,

Z-methyl-S-laurylimino2-pyrroline,

1-lauryl-2-imino-5-methylenepyrrolidine,

2,4-diheXyl-5-laurylimino-4-methyl-2-pyrroline,

' 2,4-dihexyl-5-laurylimino-4-methyl-1-pyrroline,

3-hexyl-2-imino-1-lauryl-3-methyl-5rhexylidenepyrrolidine, 4-methyl-2,4-diphenyl-5-laurylimino-Z-pyrroline,

. 1-benzyl-2-benzylimino-3,3-dimethyl-5-methylenepyrroliindole 2,4,4-trimethyl-5 -octadecylimin0-2-pyrroline, 3 ,3-dirnethyl-2-imino-1-octadecyl-S-methylenepyrrolidine, 2,3 -dirnethyl-5 -octadecylimino-Z-pyrroline, 2,3-dimethyl-S-octadecylimino-1-pyrroline, 1-octadecyl-2-irnino-4-methyl-S-methylenepyrrolidine, 4-methyl-2,4 dicyclohexyl-5 -octadecylimino-2-pyrroline, 3 -cycloheXyl-ZZ-imino-B-methyl-1octadecyl-5-cyclohexylidenepyrrolidine, 5-octadecylimino-4-rnethyl-2,4-dicyclohexyl-1-pyrroline, 2-octadecylimino-3,3 ,6-trimethyl-2,3,4,5,6,7-hexahydroindole, Z-imino-1-octadecyl-3,3,6-trimethyl-2,3,4,5 ,6,7-hexahydroindole, 2,4,4-trimethyl-5-methylimino-2-pyrroline, 1-ethyl-2-imino-3 ,3 -dimethyl-S -methylenepyrrolidine, 2,4,4-trimethyl-5 -butylimino-2-pyrroline, 1-butyl-2-imino-3 3 -dimethyl-5 -methylenepyrrolidine, 2,4,4-trimethyl-5-benzylimino-2-pyrroline, l-benzyl-2-imino-3 3 -dimethyl-5 -methylenepyrrolidine, 2,4,4-trimethyl-5- 3 -metl1oxypropylimino -2-pyrroline, 1- 3-methoxypropyl) -2-i1nino-3,3-dimethyl-5-methylenepyrrolidine, 2,4-dimethyl-4-ne op entyl-S 3 -diethylaminopropylimino)-2-pyrroline, 1- 3-diethylarninopropyl) -2-imino-3 -methyl-3-neopentyl 5 -methylenepyrrolidine, 4-methyl-4-ethyl-2-propyl-5 (2-methyl-2-hydroxypropylimino)-2-pyrroline, 1- (2-methyl-2-hydroxypropyl) -2-imino-3-methyl-3 -ethyl- 5 -propylidenepyrrolidine, 2,4,4-trimethyl-5 -phenylimino-2-pyrrolme, '1-phenyl-2-imino-3 3 -dimethyl-5 -methylenepyrrolidine, 2,4,4-trimethyl-5 -p-tolylirnino-2-pyrroline, 2-p-tolylimino-3 ,3 -dirnethyl-5 -methylenepyrrolidine,

- 2-a-naphthylimino-3,3-pentamethylene-2,3,4,5,6,7-hexa- 2-hydroXy-2,4,4-trimethyl-S-methyliminopyrrolidine,

2-allylirnino-3,3-pentamethylene-7a-hydroxy-Z,3,3a,4,5,

6,7,7a-octahydroindole,

2- (2-ethoxyethylimino -7 a-hydroxy-3 ,3 ,6-trimethyl-2,3

321,4,5,6,7,7a-octahydroindole,

1-benzyl-5-benzylimino-2,4,4-trimethyl-2-pyrroline,

dine, 1-benzyl-5-benZylimino-2,3-dimethyl-2-pyrroline, 1-benZyl-2-benzyliinino-4-methyl-S-methylenepyrrolidine, 1-benzyl-5-benzylimino-2,4-diheXyl-4-methyl-2-pyrroline, 1-benzyl-2-benzylimino-3 -heXyl-3-methyl-5-hexylidenepyrrolidine, 1:benzyl-S-benzyliminor2,4-bis (Z-methylpropyl) -4-rnethyl-2-pyrroline, l-benzyl- 2-benzylimino-3 -methyl-3 (2-'nethylpropyl) -5 (Z-methylpropylidene) pyrrolidine, l-benzyl-S -benzylimino-2,4-dimethyl-4-(2,2-di1nethylpropyl) -2-pyrroline,

' 1-benzyl-2-benzylimino-3-methyl-3-(2,2-dirnethylpropyl) 5 -methylenepyrrolidine,

' 1-butyl;5 butylimino-2,4,4-trirnethyl-2-pyrroline,

1 butyl-2-butylimino-3,3-dimethyl-5-methylenepyrrolidine, 1-butylimino-2-butyl-3 -methyl-l ,4,5,6,7,7a-hexahydroisoindole, I spiro{3,3-dimethylbicyclo(2.2.1)heptane-2,4 [1'-butyl- 2'-methyl-5 -butylimino-2'-pyrroline] I 1-butyl-2-butylimino-3,3,6-trimethyl-2,3,4,5,6,7-hexahydroindole, 1-dodecyl-S-dodecylirhino-ZA,4-trimethyl-2-pyrroline, 1-dodecyl-2-dodecylimino-3,3-dirnethyl-5-Inethylenepyrrolidine,

1-p tolyl-2-p-tolylimino-3,3-pentamethylene-2,3,4,5,6,7-

hexahydroindole,

1- 2-butoxyethyl -2- (2-butoxyethylimino -3, 3 -p entamethylene-2,3,4,5,6,7-hexahydroindole,

1- 3-dimethylaminopropyl) -2- 3 -dimethylaminopropyl-' imino -3 3-pentamethylene-2, 3 ,4,5, 6, 7-hexahydroindole,

1-hexadecyl-5-hexadecylimino-2,4-dimethyl-4- 2,2-dimethylpropyl) -2-pyrroline,

1-hexadecyl-2-hexadecylimino-3 -methyl-3 2,2-dimethylpropyl --me thylenepyrrolidine,

1-(2-ethy1aminoethyl) -5-(2-ethylaminoethylimino) -2,4-

dimethyl-4- 2,2-dimethylpropyl) -2-pyrroline,

1-( Z-ethylaminoethyl) -2- (2-ethylaminoethylimino) -3- methyl-3- (2,2-dimethylpropyl) -5 -methylenepyrrolidine,

.1-(2-phenylethyl) -5- 2-phenylethylimino -2,4-dimethyl- 4- 2,2-dimethylpropyl) -2-pyrroline,

1- 2-phenylethyl) -2- (phenylethylimino -3 -methyl-3- (2,2-dimethylpropyl) -5 -methylenepyrrolidine, and

1-dodecyl-2-imino-3,3-dimethyl-5-methylenepyrrolidine.

Typical reactants having the formula HX include hydrocyanic acid, Water, methanol, ethanol, propanol, 2-

.methylprop anol, 2,2-dimethylpropanol, l-butanol, 2-ethylhexanol, l-octanol, l-dodecanol, l-octadecanol, benzyl alcohol, fi-phenylethanol, 3-dimethylamino-l-propanol, Z-dibutylaminoethanoL- 3-butylaminopropanol, Z-methoxyethanol, Z-butoxyethanol, Z-methoxy-l-propanol, cyclohexanol, furfuryl alcohol, tetrahydrofurfuryl alcohol, tetrahydrobenzyl alcohol, 2-norcamphanylmethanol, 2- norcamphenylmethanol,

Z-rnethyl- 2-vinoxyeth- 2-phenoxyethanol,

mercaptoethanol, 2-butylmercaptoethanol,

.anol, 2-vinylmercaptoethanol, allyl alcohol, crotyl alcohol, a-naphthylmethanol, ,B-naphthylmethanol, hydrogen sulfide methyl mercaptan, butyl mercaptan, cyclohexyl mercaptan, phenyl .mercaptan, benzyl mercaptan, 2-metl1- foxyethyl mercaptan, 2-ethoxyethyl mercaptan, Z-butoxyethyl mercaptan, 2-phenoxyethyl mercaptan, dodecyl mer captan, hexadecyl mercaptan, octadecyl mercaptan, 2- methoxypropyl mercaptan, 2-butoxypropyl mercaptan,

Z-butoxybutyl mercaptan, 2-butoxycyclohexyl mercaptan,

methyl fi-mercaptopropionate, B-mercaptopropionitrile, ethylene glycol, diethylene glycol, propylene glycol, trimethylene glycol, tetramethylene glycol, 2-ethyl-1,3-hexanediol, ethanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 1,2-butanedithiol, 1,3-butanedithiol, 1,4-butanedithiol, butenediol, butynediol, ammonia, methylamine,

butenylamine, benzylamine, ethylbenzylamine, dodecylphenylpropylamine, ethoxybutylamine, ethanolamine, and

3-dirnethylaminopropylamine.

It should be noted that in the HX reactant when X stands for R NH, the nitrogen atom must be attached to a hydrogen atom or to a carbon atom that is in turn attached to no more than two other carbon atoms. Similarly, it should be noted when X stands for R' A. Otherwise, the present reaction is sterically hindered and not readily consummated.

. When X represents R' A, it is preferred to employ the R' AH reactant in excess of the amount required, in order to assure completeness of reaction and maximum yields. The reaction temperature ranges from normal room temperature (about 20 C.) to about 75 C., preferably about 20 to 60 C. The reaction is readily conducted without the use of a solvent but if such is desired, there may be employed an inert voltatile organic solvent, such as benzene, toluene, Xylene, heptane, hexane, methylene chloride, chloroform, and the like. The products formed are eithercrystalline solids or viscous liquids. The products do not require any purification, although selective extraction or recrystallization from a solvent suchas octane may be employed if a productof high purity is desired.

When X represents R NH, it is preferable to employ the R NH reactant in excess of the amount required in order to assure completeness of reaction and maximum yields. The reaction temperature ranges from about 0 to somewhat below 75 C., such as 70 C., preferably about 20 to 60 C. The reaction may be conducted in the presence of an inert volatile organic solvent, such as benzene, toluene, xylene, heptane, hexane, methylene chloride, chloroform, and the like. The product formed is frequently crystalline in nature and may be separated by filtration and purified by recrystallization from a suitable solvent, such as the hydrocarbonsolvents, as desired;

The course and completeness of the reaction is readily followed by use of the infrared absorption spectra and and it has been repeatedly observed that infrared bands characteristic of the reactants disappear as the reaction reaches completion. This is frequently a valuable aid in determining the rate and extent of the present reaction as will be apparent to one skilled in the art.

While the present reaction is consummated by a mere mixing of the selected reactants, it is frequently advantageous to add from 0.1 to 10.0 mole percent of an acid in order to expedite the reaction. This acid may be employed as the acid salt of the amine reactant and such is the preferred way. The common laboratory acids are satisfactory, economical and, therefore, preferred in this respect. Suitable for this use are hydrochloric, hydrobromic, sulfuric, and the like, preferably in the form of the salt of the amine reactant.

It is possible, if desired, in some instances such as with ammonia and methyl'amine to prepare the present compounds by reacting a ketonitrile having the formula with the amine reactants previously discussed in a molecular ratio of substantially one the latter. a

The present compounds are prepared by reacting an equivalent of the definedheterocyclic reactant with substantially an equivalent of hydrocyanic acid. The present reaction is conducted at atmospheric pressures and of the former to two of at a temperature range of 0 to C., preferably, at

While no catalyst is actually required, as statedheretofore, it may be advantageous in some instances to supply a cyanide ion generating catalyst in which caseth'e catalyst is employed preferably inarnounts of about 0.1 to 20% by weight of the total-weight of the reactants. Suitable as a catalyst are alkali metals and their carbonates, the lower alkoxides, oxides, hydroxides, peroxides, and cyanides of the alkali metals and alkalineearth metals,

tertiary amines, and quaternaryammonium bases. Ac-

tually there may be employed as catalyst any base whose aqueous 0.1 molar solution has a pH of about at least 9.

Typical examples of the catalyst that maybe used are sodium, potassium, lithium, sodium methoxide, potassium butoxide, lithium ethoxide, magnesium ethoxide, sodium oxide, potassium hydroxide, calcium oxide, barium hydroxide, strontium hydroxide, sodium peroxide, magnesi- .um peroxide, potassium cyanide, lithium cyanide, barium cyanide, magnesium cyanide, sodium carbonate, potassium carbonate, trimethylamine, triethylamine, triethanolamine, octyldimethylamine, N-methylmorpholine, benzyltrimethylammonium hydroxide, dibenzyldimethylammoany convenient particle size.

nium hydroxide, dodecenyltriethylammoniumhydroxide, and the like. The alkali metal cyanides are particularly effective for the instant purposes. g

It is advantageous to introduce the hydrocyanic acid at such a rate that reaction occurs promptly and the rate of introduction may be. regulated. so as to substantially equal the rate of reaction as will be clear to one skilled in the Under such circumstances, no adverse side reactions are noticed and high yields are obtained frequently approaching 100 percent. Hydrocyanic acid may be introduced into the reaction mixture in either the gaseous or liquid state as is desired and substantially similar results are obtained in either case. The rate of addition of hydrocyanic acid varies with the temperatures at which the reactions are carried out. When high temperatures are employed, reaction times may be shortened from hour-s to minntes,pamt=iculanly when high molecular weight pyrroline starting materials are employed.

If desired, a volatile inert organic solvent may be employed in order to obtain maximum reaction benefits. The solvent may be of the hydrocarbon type, such as hexane,

when the reaction was conducted for prolonged periods a retention reaction vessel and add hydrogen until a certain hept-ane, benzene, toluene, and the like, or it may be selected from the class of secondary and tertiary alcohols, others, substituted amides, nitriles, and halogenated hydrocarbons, as desired. At the conclusion of the reaction, the product may be isolated by neutralization of any catalyst which had been added, separation from the salts so formed and removal of volatile solvents and the starting materials. Further purification may be accomplished by selective extraction, distillation, or crystallization, whichever is appropriate, as is conventional for anyone skilled in the art.

The products in which X represents an aminomethyl group are prepared by hydrogenation from the corresponding products where a cyano group.

The hydrogenation is car'ri d out n the presence of a catalyst. Suitable as catalysts are Raney nickel, Raney cobalt, cobalt with ammonia, nickel with ammonia, cobalt-copper, nickel-cobalt, palladium, platinum, ruthenium, and the like. The catalyst may be employed in Generally, the smaller particle sizes produce thehi-gher rates. desired, the catalyst may be deposited on a carrier material in order to extend and activate it. Suitable for use as a carrier are activated alumina, activated clays, silica gel, charcoal, asbestos, pumice, and the like. Room temperatures and somewhat above may be employed when a noble metal is used as the catalyst. When the other materials are employed as catalyst, temperatures in the range of about 75 to 250 C. are employed with about 100 to 200 C. preferred. it is preferred that the hydrogenation be carried out at the lowesttemperature at which reduction can occur within the ranges previously set out. An inert, volatile, organic solvent may be desirable, such as hydrocarbons, alcohols, others, and the like. The lower allcanols, such as methcool or ethanol, are particularly suited for this use. When the noble metals are used as catalysts, a small amount 0t an activating acid, such as acetic or hydrochloric, may be employed.

Pressures in the range of atmospheric to 10,000 p.s.i.g. are employed. Actually, higher pressures may be used if desired but in most instances, no apparent advantages are achieved for the extra elfort extended. The reaction shown proceeds a little more rapidly at the higher pressures but lower pressures may be successfully employed with some of the catalysts, especially Raney nickel. The preferred range of pressures is atmospheric to 100 P.S.'i.g. when noble metal catalysts are employed and 0 to 5000 p.s.i.g. when the transition metal catalysts are used.

The present reaction should be concluded as soon as one mole of hydrogen has reacted. Otherwise, if the reaction is conducted tor periods of time that are substantially longer than that required for one mole of hydrogen ring may occur. In some instances, this has been observed desired pressure is reached. The reaction vessel or at leastthe reactioningredients may be preferably agitated such as by shaking or rotating until a precalculated drop in pressure is observed. This significant drop in pressure indicates that an equivalent amount of hydrogen has reacted. This precalculated pressure drop, indicating that an equivalent amount of hydrogen has reacted, is readily calculable by known methods. Therefore, an indication of reaction completion may be readily calculated and observed. I

At the conclusion of the reaction, the product is obtained by filteringofi the catalyst and stripping oil the solvent. If desired, the products may be purified by distillation or recrystallization from hydrocarbons, others, or the like.

The compounds of this invention have been presented in their free-base form and in this free-base form, they possess the valuable characteristics and concurrent utilities previously referred to. However, it is to be construed that the present invention includes the acid addition salts of these tree-base products also. It is desirable, in some instances, to employ the present products in their watersoluble salt term. For instance, in pesticidal applications, it is highly-desirable to deal with watensoluble compounds in order that satisfactory spray solutions may be formulated. In other applications, wherein any physiological benefits are desired, it is frequently advantageous to employ the present products in their organic salt form in order to provide substantial neutrality with stability.

In orderto prepare the salt forms of the present compounds, it is necessary only toreact these compounds with a stoichiometric amount of the selected acid. The salt formation occurs readily at room temperature without the aid of a catalyst. If solid reactants are employed, it may be advantageous to use an inert volatile solvent such as benzene, toluene, xylene, hexane, heptane, methylene chloride, chloroform, or the like. The solvent can then be readily removed at the conclusion of the reaction by conventional methods. The salt product does not require any further purification although recrystallization from a solvent such as isooctane may be resorted to if a product of high purity is demanded.

' to react, there is some chance that hydrogcnolysis of the While it is believed clear to one skilled in the art from the above description how the salts are prepared, such salt formation may be specifically illustrated by indicating that one would take an equivalent amount of a selected compound of this invention in its free-base form and then add a stoichiometric amount'of a selected acid which would, for instance, be 36.5 parts of hydrochloric acid, 98 parts of sulfuric acid, 60 parts of acetic acid, 72 parts of acrylic acid, and the like. The corresponding hydrochloric, sulfuric, acetic and acrylic acid salts respectively are readily formed. Similarly, othersalt products may be prepared. 1

The products of the present invention are useful as fungicides, particularly when applied against Monilina fructicola and Stemphyliu'm sarcinneforme. Complete inhibition is frequently observed in concentrations of about 0.1% and lower and many of the compounds are effective in concentrations as low as 0.01% and lower when applied filed March 3, 1958, and 742,726 and 742,753, filed June 18, 1958, all of which are now abandoned.

The compounds of this invention, as well as the methods for their preparation, may be more fully understood from the-following examples which are ofiered by way of illustration and not by way of limitation. Parts by weight are used throughout.

V Example 1 Hydrogen cyanide (4 parts) is added dropwise to 1- butyl-S-butylimino-2,4,4-trimethyl-2-pyrroline (24 parts). An exothermic reaction occurs. The mixture is then stirred for one hour and the excess hydrogen cyanide is then removed by stripping under reduced pressure. f The product has a boiling point of 114 to 115 C. (0.9 mm.), an ii value of 1.4710, and is obtained in a 70% yield (17:5 parts). The product contains 16.01% nitrogen (theoretical 15.95%), 73.12% carbon (theoretical 72.94%), 11.16% hydrogen (theoretical 11.10%). The infrared spectrum confirms the structure of the product as 2-cyano-1-butyl-5-butylimin0-2,4,4-trimethylpyrrolidine.

The same product is obtained by reacting hydrocyanic ,acid with 1-butyl-2-butylimino-3,3-dimethyl-5-methylenepyrrolidine.

In similar fashion are prepared 2-cyano-1-dodecyl-5- dodecylimino-2,4,4-trimethylpyrrolidine from l-dodecyl- 5 dodecylimino-2,4,4-trimethyl-2-pyrroline, l-benzyl-S- benzylirnino 2-cyano-4-methyl-2,4-bis(2-methy1propyl) pyrrolidine from 1-benzyl-S-benzylimino-4-methyl-2,4- .bis, (2 methylpropyl)-2-pyrroline, 2-cyano-1-hexyl-5- hexylimino 2,4 bis (Z-methylpropyl)-4-methylpyrrolidine from 1-hexyl-5-hexylimino-2,4-bis-(Z-methylpropyl)- 4 methyl-Z-pyrroline, 1-butylimino-2-butyl-3-cyano-3- methyl-1,3,3a,4,5,6,7,7a-octahydroisoindole from l-butylimino 2 butyl-3-methyl-1,4,5,6,7,7a-hexahydroisoindole, and 1-(2-butoxyethyl)-2-(2-butoxyethylimino)- 7a cyano' 3,3 pentamethylene-2,3,3a-4,5,6,7,7a-octahydroindole from 1-(2-butoxyethyl)-2-(2-butoxyethylimino)-3,3-pentamethylene-2,3,4,5,6,7-hexahydroindole.

Example 2 To a solution of 1-(2-hydroxyethyl)-5-(2-hydroxyeth ylimino).-2,4,4-trimethyl-2-pyrroline (53 parts) dissolved in acetonitrile (50 parts) is added hydrogen cyanide (9 parts) in a dropwise manner. maintained at 70 to 82 C. for two hours. .Excess hydrogen cyanide and the acetonitrile solvent are removed by stripping under reduced pressure. The residue crystallizes on cooling and recrystallized from ether to give the product, 2-cyano-1-(Z-hydroxyethyl)-5-(2-hydroxyethylimino)-2,4,4-trimethylpyrrolidine, having a melting point of 87 to 89 C. Recrystallization from benzene gives the analytical sample having a melting point of 915 to 92 C. The product contains 17.6% nitrogen (theroretical 17.6%), 60.4% carbon (theoretical 60.2%), and 8.9% hydrogen (theoretical 8.8%). The yield of recrystallized product is 60% of the theoretical. Examination of the spectrum in the infrared range supports the stated structure.

. The same product is obtained by reacting hydrocyanic acid with 1-(2-hydroxyethyl)-2-(2-hydroxyethylimino) 3,3-dimethyl-5-methylenepyrrolidine. In asimilar fashion are prepared l-butyl-5fbutylimiho- 2-cyano-2,4,4-triethylpyrrolidine from 1 butyl-5-butylimino-2,4,4-triethy1-2-pyrroline, 7a-cyano-1-(3-dimethylaminopropyl) 2-(3 dimethylaminopropylimino) -3,3-pentamethylene-2,3,3a,4,5,6,7,7a-octahydroindole from 1-(3-dimethylaminopropyD 2 (3 dimethylaminopropylimino)-3,3-pentamethylene-2,3,4,5,6,7-hexahydroindole, and 2 cyano 1 (2 ethylaminoethyl)-5-(2-ethylaminoeth ylirnino) 2,4 dimethyl-4-(2,2-dimethylpropyl)-pyrrolidine from 2,4-dimethyl-4-(2,2-dimethylpropyl)-1-(2aethylarninoethyl) -5-( Z-ethyIaminoethyIimind -2-pyrroline. Example 3 I Hydrogen cyanide (2 parts) is added to 3,3-dimethyl-2- imino-1-lauryl-5-methylenepyrrolidine 12 parts) (in;

The reaction mixture is 1.4782the liquid isomer). The reaction mixture is stirred for thirty minutes after the addition is complete and the mild exotherm has subsided. Unreacted hydrogen cyanide is removed by stripping under reduced pressure. The product contains 11.68% nitrogen (theoretical 13.15%), 67.24% carbon (theoretical 75.18%), and 11.96% hydrogen (theoretical 11.67%). This analysis indicates that the reaction has proceeded to convert 60% of the iminopyrroline to the cyanopyrrolidinel Distillation of a portion of the stripped material shows that the product can be distilled but that separation of the starting material from the final product is not easily carried out by simple distillation. The product has a boiling point of 164 to 172 C. (0.8 mm.) and has an n value of 1.4738. The sample contains 12.02% nitrogen. This corresponds to a mixture of 68% of the cyanoiminopyrrolidine and 32% of the starting iminopyrroline.

The same product is obtained by reacting hydrocyanic acid with 5-irnino-1-lauryl-2,4,4-trimethyl-2-pyrroline.

In a similar fashion, 5-benzylimino-2-cyano-2,4,4-trimethylpyrrolidine is prepared from 5-benzylimino-2,4,4- trimethyl-2-pyrroline. In this case, too, the reaction does not go to completion and separation from the starting material is diflicult. The product has a boiling point of to 166 C. (1.4 mm.), and an n value of 1.5447.

-The product contains 15.7% nitrogen (theoretical 17.4%)

and has a neutral equivalent of 237 (theoretical 241). The infrared absorption spectra in both of these instances confirms the conclusion that in each instance the reaction has not been forced to go to completion and'absorption bands corresponding to both the starting material and the final product are easily recognized.

Example 4 A much purer product is obtained from the addition of hydrogen cyanide to 5-cyclohexylimino-2,4,4-trimethyl-2- pyn'roline. In this instance, hydrogen cyanide (4 parts) is added dropwise to 5-cyclohexylimino-2,4,4-trimethyl-2- pyrroline (30 parts). The raction mixture is allowed to stand overnight at room temperature. The reaction mixture is thendistilledto give the product, having a boiling point of 117 to 127 C. (0.2 mm.) (16 parts) which solidifies in the receiver. The product contains 17.4% nitrogen (theoretical 18.0%). Only small amounts of the starting 5-cyclohexylirnino-2,4,4-trimethyl-2-pyrro1ine are present in the product and are recognized by inspection of the infrared absorption spectrum of the product.

The same product is obtained by reacting hydrocyanic acid with 2-cyclohexylimino-3,3dimethyl-5-methylenepyr- Example 5 Hydrogen cyanide (3 parts) is added to a slurry of 5-laurylimino-2,4,4-trimethyl-l-pyrroline (15 parts) (the solid isomer) in dimethyl formamide parts). Pyridine hydrochloride (0.1 part) is added when the reaction appears to be sluggish. The mixture becomes homogeneous one-half hour after the addition of the catalyst. Ex-

amination of the spectrum of the reaction mixture in the infrared range 24 hours after the materials are combined -shows that Z-cyano-5-laurylimino-Z,4,4-trimethylpyrrolidine has formed.

. Example 6 p L 1-butyl-S-butylirhino-Z-cyano-2,4,4-trimethylpyrrolidine 1 1 (12 parts) and Raney nickel (1 part) are'heated at150 160 C. is a hydrogen atmosphere at 1750 p.s.i.g. tor 1.5 hours in a rocking autoclave. The bomb is cooled and vented and the reaction mixture is filtered to separate it from the'catalyst. 'The filtrate is distilled under reduced pressure to give the. product, Z-aminomethyl-l-butyl-S- butylimino-2,4,4-trimethylpyrrolidine, having a boiling point of 123 128 C. (2.0 mm.) and an 11 value of 1.4784. The product contains 71.70% carbon (71.85% theoretical), 12.48% hydrogen (12.44% theoretical), 15.3% nitrogen (15.7% theoretical), and has a neutral equivalent of 144.5 (134 theoretical).

In like manner, there are prepared 2-aminomethyl-1- heXyl 5 heXylimino-2,4-bis-(Z-methylpropyl)-4-methyl pyrrolidine from 2-cyano-1-hexyl-5-hexylimino-2,4-bis-(2- methylpropyl)-4-methylpyrrolidine, Z-aminomethyl-S-butylimino-2,4,4-trirnethylpyrrolidine from Z-cyano-S-butylimino-2,4,4-trimethylpyrrolidine, and Z-aminomethyl-S- dodecylimino 2,4 dimethyl-4-(2,2-dimethylpropyl)pyrrolidine from 2-cyano-2,4-dimethyl-4-(2,2-dimethylpropyl)pyrrolidine. Similarly, there are prepared 7a-aminomethyl 2 butylimino-3',3,6-trimethyl-2,3,3a,4,5,6,7,7a-

octahydroindole from 2-butylirnino-7a-cyano-3,3,6-trimethyl-2,3,3a,4,5,6,7,7a-octahydroindole, spiro {3,3,-dimethylbicyclo (2.2.1)-heptane-2,4-[2'-aminomethyl-1'- butyl-S'-butylimino-2'-rnethylpyrrolidine]} from spiro {3,- 3-dimethylbicyclo (2.2.1 -heptane-2,4'- 1'-butyl-5 -butyl imino-2'-cyano-2-methylpyrrolidine]}, and S-aminomethyl 2 butyl-1-butylirnino-3-methyl-1,3,3a,4,5,6,7,7a-octahydroisoindole from Z-butyl-1-butylimino-3-cyano-3- methyl-1,3,3a,4,5,6,7,7a-octahydroisoindole.

Example 7 Hydrogen cyanide (3 parts) is added to a slurry of S-Iaurylimino-ZA,4-trimethyl-l-pyrroline parts) the solid isomer) in dimethyl formamide (150 parts). Pyridine hydrochloride (0.1 part) is added when the reaction appears to be sluggish. The mixture becomes homogeneous one-half hour after the addition of the catalyst. Examination of the spectrum ofthe reaction mixture in the roline in the presence of one mole percent of their hydrochloridesascatalyst's to give 2-dodecylamino-5-butylimino-2,4,4-trimethylpyrrolidine,

2-( Z-rnethoxypropylamino) -5 -butylimino-2,4,4-trimethylpyrrolidine,

2- (Z-hydroxyethylamino) -5 -butylirnino-2,4,4-trimethylpyrrolidine, and

2- 3 -dirnethylaminopropylamino) -5 -butylimino-2,4,4-

' trimethylpyrrolidine, respectively.

Similarly, Z-ethylhexylarnine, cyclohexylamine, and

allylamine are added to 5-cyclohexylimino-2,4-dimethylinfrared range 24 hours after the materials are combined I Example 8 Benzylamine hydrochloride (0.2 part), S-benzylimino- 2,4,4-trimethyl-2-pyrroline (43 parts), and benzylamine (21.5 parts) are mixed and allowed to stand for four days at room temperature. The infrared absorption spectrum of the mixture establishes the absence of significant amounts of either of the starting materials. The bands at. 1683 cmr 1608 cm? and 1582;cm. which are characteristic of the benzyliminotrimethylpyrroline are missing from the spectrum. There is a single band at 3220 cmin the NH stretching region. If unreacted benzylamine were present, there would be two bands in the 3300-3500 cm.- region. A strong band appears at 1627-1640 cmf This band is characteristic of 5-alkylimino-2,4,4-trimethylpyrr0lidines which carry substituents in the 2-position. The product is identified as 2-benzylamino'-5-benzylimino-2,4,4-trirnethylpyrrolidine.

The same compound is prepared by reacting benzylamine with 2-benzylimino-3,S-dimethyl-S-methylenepyrrolidine.

In a similar fashion, dodecylamine, 2-methoxypropy1- amine, Z-hydroxyethylarnine and B-dimethylaminopropylamine are added to 5-butylimino-2,4,4-trimethyl-2-pyr- '1 the reactor is vented and the bomb contents are stripped 4-(2-2-dimethylpropyl) 2-pyrroline in the absence of a catalyst to give 2- ethylhexylamino -5 -cyclohexylimino-2,4-dimethyl-4- (2,2-dimethylpropyl)pyrrolidine, 2-cycloh'exylamino-5-cyc1ohexylimino-2,4-dimethyl-4- (2,2-dimethylpropyl)pyrrolidine, and 2allylamino-5-cyclohexylirnino-2,4-dimethyl-4- (2,2-

dimethylpropyl)pyrrolidine.

Likewise, 3,3,6 trimethyl 2,3,4,5,6,7 hexahydro 2-(3- methoxypropylimino)indole is reacted with ethylamine to .give 2-(3 methoxypropylimino)-3,3,6-trimethy1-7a-ethylamino-2,3,3a,4,5,6,7,7a-octahydroindole.

Example9 When either methylamine or ammonia is employed, it is convenient to charge an excess of either of these together with the selected iminopyrroline to a pressure vessel and allow the reaction mixture to stand for several days. The vessel is warmed to'50 or 60 C. in order to hasten the process. The vessel is then cooled and vented to the atmosphere and the product is isolated.

'In this fashion, methylamine is reacted with 1-methyl-3-methylimino-3,3a,4,5,6,7-hexahydroisoindole,

2-methylimino-3,3-pentamethylene-2,3,4,5,6,7-

hexahydroindole, and V 5-octadecylimino-2,4,4-trimethyl-Z-pyrroline to give, respectively,

1-rnethylamino-1-methyl3-methylimino1,3,3a,4,5,6,7,7a-

octahydroisoindole,

3,3-pentamethylene-2-methylimino-7a-methylamino- 2,3,3a,4,5,6,7,7a-octahydroindole, and

, 2-methylamino-2,4,4-trimethyl-S-octadecyliminopyrrolidine.

Similarly, ammonia and,

5 -laurylimino-2,4-dimethyl-4-( 2,2-dimethylpropyl -2- pyrroline,

2,4-bis (Z-methylpropyl) -4-methyl-S-methylimino-Z- pyrroline, and

V 2,4-diphenyl-4-methy1-5methylimino-2-pyrroline give, respectively,

2-amino-2,4-dimethyl-4- 2,2-di1nethylpropyl) -5 lauryliminopyrrolidine,

2-amino-2,4-bis(Z-methylpropyl) -4-methyl-5- methyliminopyrrolidine, and.

, 2-amino-2,4-diphenyl-4-methyl-5-methyliminopyrrolidine.

Example 10 In the case of both methylamine and ammonia, it has been foundpossible to prepare the compounds of this invention directly "from ketonitriles. Thus, 2,2-dimethyl 4-oxopentanonitri1e (63 parts), and methylamine (74 parts) are combined in a Dry-Ice cooled pressure reactor. The reactor is sealed and allowed to warm to room temperature. After standing three days at room temperature,

at reduced pressure and room temperature to remove any low boiling materials. The residue is leached with cold diethyl ether and the solid product is recrystallized from diethyl ether to give Z-methylamino-S methylimino-2-4,4- trirnethylpyrrolidine- (38 parts). i I

a neutral equivalent of 89.1 (84.5 theoretical). A second crop of crystals (6.4 parts) is separated from the mother liquors after most of the diethyl ether has evaporated. The

total yield of recrystallized product is 41% based on ketonitrile starting material; From the filtrate is recovered a 35% yield of -methylimino-2,4,4-trirnethyl-2- pyrroline having a boiling point of 90-100 C. at mm. absolute pressure and a neutral equivalent of 128.4 (138 theoretical). Both reaction products on catalytic hydrogenation over Raney nickel in methanol solution gave S-methylimino- 2,4,4-trimethylpyrrolidinein yields of approximately 90% (melting point 10811l.5 C.).

In a similar fashion, 1-(2-oxooyclohexyl)-cyclohexanecarbonitrile and 2-methyl-2-hexyl-4-oxodecanonitrile and ammonia give 7a amino-2-imino-3,3-pentamethylene- 2,3,3a,4,5,6,7,7a-octahydroindole and 2,4-dihexyl-4-methyl-5-imino-2-aminopyrrolidine, respectively. Likewise, methyl-amine and Z-acetylcyclohexane-carbonitrile give 1- methyl l-methylamino-3-methylimino-1,3,3a,4,5,6,7,7aoctahydroisoindole, and "spiro' [3,3 dimethylbicyclo- (2.2.1)heptane 2,4 (2' methyl 2' methylamino 5'- methyliminopyrrolidine)] is obtained by the reaction of methylamine and 3,3-dimethyl-2-(2-oxopropyl)-bicyclo- (2.2.1 heptane-Z-carbonitrile.

Example 11 Butyl mercaptan (18 parts) is added dropwise with stirring to 5-benzylimino-2,4,4-trimethyl-2 pyrroline (46 parts) which contains sodium 'methoxide (0.2 parts) as catalyst. The temperature of the reaction mixture rises from25 to 35 C. during the course of this addition.

The reaction mixture is warmed in an oil bath until the last traces of solid dissolves at 70 C. Theoil bath is removed and stirring is continued for several hours. The infrared absorption spectrum of the product shows a strong band at 1615-1620 c'm. The presence of this band and the absence of bands 1683 cm.- 1608 cmf and 1582 GEL-1, characteristic of the starting 2-pyrroline reactant, and the absence of bands in the 25002600 CHI-"'1, the 8-H stretching region, show that the resulting liquid product is 5 benzylimino-2-butylthio-2,4,4-trimethylpyrrolidine.

The same compound is prepared by reacting butyl n1ercaptan with 2-benzylimino-3,3-dimethyl-5-methylenepyrrolidine. I

In the same manner, 5-benzylimino-2,4,4-trimethyl-2- pyrroline reacts with methyl mercaptan, phenyl mercaptan, cyclohexyl mercaptan, dodecyl mercaptan, and octajdecyl mercaptan to give Z-methylthio-5-benzylimino-2,4,4-trimethylpyrrolidine, 2-phenylthio-5-benzylimino-2,4,4-trimethylpyrrolidine, 2-cyclohexylthio-5-benzylimino-2,4,4-trimethylpyrrolidine, i 2-dodecylthio-S-benzylimino-2,4,4-trimethylpyrrolidine, and 1 Z-octadecylthid-S-benzylimino-2,4,4-trimethylpyrrolidine,

respectively.

When gaseous hydrogen sulfide is bubbled into 5- benzylimino-2,4,4-trimethy1-2-pyrroline and the reaction mixture is allowed to stand overnight in the presence of 2 mole percent of sodium hydrosulfide catalyst, the corre- 14 7a-phenylthio-2-cyclohexylimino-3,B-pentamethylene- 2,3,3a,4,5,6,7,7a-octahydroindo1e; and l-dodecylimino-Ei-methyl-1,4,5,6,7,7a-hexahydroisoindole and ben zylmercaptan give 1-dodecylimino-3-methyl-3-benzylthio-1,3,3a,4,5,6,7,7a-

' octahydroisoindole. i

Example 12 A. Water 10 parts) and 5-benzylimino-2,4-trimethyl-2-pyrroline (46 parts) are combined and allowed to stand at room temperature in a stoppered flask. The flask is shaken occasionally to keep the reaction mixture emulsified. After six days, benzene (40 parts) is. added and the mixture is heated at 40 C. until all the solid dissolves. The aqueous layer is separated and discarded. A white solid separates when heptane is added to the benzene solution. The solid, after recrystallization from benzene and heptane, is found to melt at 117 to 121 C.

B. The same product is obtained as follows: 2,2-dimethyl-4-oxopentanonitrile (31.2 parts) and benzylamine (26.8 parts) are combined and allowed to stand in a 'stoppered flask at room temperature. Within one month the material becomes milky and solid begins to separate. After six months it solidifies. The solid is recrystallized from acetone to give the product (36 parts), 2-hydroxy- 5-bcnzylimino2,4,4-trimethylpyrrolidine, having a melting point of 119.5 to 123 C.

The product has a molecular weight of 243 (232 theoretical), a hydroxyl number of 250 (241 theoretical) and contains 72.6% carbon (72.4%.,theoretical), 9.0% hyof 71 to 73 C. Mixed melting points show that the product obtained by the above described methods A and B are identical.

Example 13 The procedure of Example 12A 'is repeated, except that benzene and a drop of hydrochloric acid are added initially and the mixture is heated at 40 to 50 C. until solution is complete. The product, 2-hydroxy-2,4,4-trimethyl-S-benzyliminopyrrolidine, is obtained in 85% yield on dilution of the benzene solution with heptane.

In like manner, 5-dodecylimino-2,4,4-trimethyl-2-pyrroline is converted to 2-hydroxy-5-dodecylimino-2,4,4-

trimethylpyrrolidine and 5-octadecylimino-2,4-dimethyl-4- '(2,2-dimethylpropyl) -2-pyrroline gives 2-hydroxy-5-octadecylirnino 2,4 dimethyl 4 (2,2 dimethylpropyl)- pyrrolidine. i

Example l4 When the 5-imino '2-pyrrolines have even slight solubility in water, the hydration may be accomplished by simply mixing the iminopyrrolines with water and stirring and warming until hydration is complete. This hydration reaction can be followed by noting the change in the ultraviolet absorption spectrum of the aqueous solution. The iminopyrrolines of this invention show an absorption band at 235-245 mm. When hydration occurs, this band disappears and in its place a band at 205 mm. is observed. The magnitude of the extinction coeflicients may be plotted-as a function of time to determine the rate of the reaction. Varying conditions of time and temperature and pH of the aqueous solution have been studied. When the pH of the medium is adjusted to 7 or below, the mixture becomes homogeneous owing to salt formation; the salts are much more soluble in water than are the free bases. Thus, at pH 7, 5-laurylimino 2,4,4-trimethyl-2-pyrroline is observed to hydrate to the corresponding 2-hydroxy-5-laurylimino-2,4,4-trimethylpyrrolidine to the extent of 50% after 18 hours at room temperature (the molar extinction coefficient By operating at pH 7 at room temperature, it is possible to hydrate many of the iminopyrrolines used as starting materials in this invention. Under these conditions little or no opening ofv the iminopyrrolidine ring occurs. On prolonged heating in aqueous acid solution, however, it is possible to further hydrolyze Z-hydroxy-S- alkylimino-2,4,4-trirnethylpyrrolidines to 2,2-dimethyl-4- oxopentanoic acid and the alkyl amine (as its salt). This side reaction is suppressed by operation at low temperatures. In this manner are prepared Zhydroxy-S-phenylimino 2,4,4 trimethylpyrrolidine, 2 hydroxy 2,3- dimethyl cyclohexyliminopyrrolidine,'7a hydroxy- 2 (2 ethoxyethylimino) 3,3 pentamethylene 2, 3,3a,4,5,6,7,7a'- octahydroindole, 3- hydroxy 1 laurylimino 3 methyl 1,3,3a,4,5,6,7,7a octahydroisoindole, 2 hydroxy 5 octadecylimino 4 methyl 2,4 ('2.- rnethylpropyDpyrrolidine, and 7a hydroxy' 2 nor camphanylmethylimino 3,3 dimethyl 2,3,3a,4,5, 6,7,7a-

,octahydroindole from the corresponding iminopyrrolines.

Example Alcohols react in much the same fashion as does water. These additions occur in the presence of either acidic or alkaline catalysts or in the absence of any added catalyst. The irninopyrroline starting materials are sufficiently basic to serve as their own alkaline catalysts. The reaction may be carried out by mixing stoichiometric quantities of the two reactants in the absence of a solvent or in the presence of an inert diluent or, one of the two reagents, preferably the alcohol, may be added in large excess. The latter technique is especially applicable when the lower alkanols are employed, especially if the reaction products are to be isolated as their salts. Again, as is the case when the addition of water to the iminopyrrolines is examined, the ultraviolet absorption spectrum of the reaction mixture may be employed to establish whether or not addition has occurred and to what extent the reaction has proceeded at any time. Following the procedure of Example 14, but substituting the alcohols for the water employed, adding a mole of fumaric acid and a mole of the corresponding iminopyrroline to the alkanol, warming to achieve homogeneity, and allowing to standat room temperature overnight gives: 2-rnethoxy- 5 methylimino 2,4,4 trimethylpyrrolidine, 2 ethoxy- 5 benzylimino 22,4,4 trirnethylpyrrolidine, 2 (2- 'eth ylhexoxy) 2, 3 dimethyl 5 laurylirninopyrrolidine, 2 butoxy 5 phenylimino 2,4,4 -trimethylpyrrolidine, 7a methoxy 2 cyclohexylimino 3,3-

dirnethyl 2,3,3a,4,5, 6,7,7a octahydroindole,,2 allyloxy- 5 (2 phenoxyethylimino) 2,4,4 trimethylpyrrolidine, and Q methoxy 5 benzylimino 4 methyl 2,4- bis(2-methylpropyl)-pyrrolidine as their acid fumarate salts. When hydrogen chloride is substituted for fumaric acid, the corresponding hydrochloride salts result and when methanesulfonic acid is substituted for fumaric acid, the corresponding methanesulfonates result Omission of the acid or use of minor amounts of acids as catalysts give the corresponding free bases. These products may frequently be applied as solutions in the alkanols in which they, are prepared.

Example 16 spectrum from time to time until the reaction is shown to be complete by disappearance. of the characteristic iminopyrroline peak. In this manner are prepared 2- 'dodecoxy 5 -laurylimino-2,4,4etrimethylpyrrolidine, 2-

hexadecoxy 5 octadecylimino-2-methylpyrrolidine and 16 2 -benzyloxy S-benzylimino-Z,4-dimethyl-4-(2,2-din1ethyl- 'propyl)pyrrolidine. Again, acid catalysis markedly accelerates this process.

The compounds of this invention have been presented in their free-base form and inithis free-base form, they possess the valuable characteristics and concurrent utilities previously referred to. However, it is to be construed that the. present invention includes the salts of these freebase products also. It is desirable, in some instances, to employ the present products in their water-soluble salt form. For instance, in many pesticidal applications, it is highly desirable to deal with water-soluble compounds in order that satisfactory spray solutions may be formulated. In other instances, it is frequently advantageous to employ the present products in their organic salt form in order'to provide substantial neutrality with stability.

We claim: a 1. The compound, a member selected from the class consisting of the compound having the [formula and the acid addition salts thereof, in which R and R ,3 to 18 carbon atoms, R taken individually represents a member selected from the class consisting of alkyl, phenylalkyl, cycloalkyl, phenyl, naphthyl, and allcylphenyl groups of no more than 10 carbon atoms, R taken individually represents a member selected from the class consisting of hydrogen and alkyl groups of 1 to 4 carbon atoms, R and R taken individually represent members selected from the class consisting of hydrogen, alkyl, cycloalkyl, phenylalkyl, phenyl, naphthyl and alkylphenyl groups of up to 10 carbon atoms, R and R taken collectively with the carbon atoms to'iwhic'h they are joined form a carbocyclic ring of 5 to 6 carbon atoms free of aromatic unsaturation including alkyl substituents of a total of no more than 4 additional carbon atoms, R and R taken collectively with the carbon atoms to which they are joined form a carbocyclic ring of 5 to 6 carbon atoms free of aromatic unsaturation including alkyl substituents of a total of no more than 4 additional carbon atoms, R and R taken collectively with the carbon atoms to which they are joined form a carbocyclic ring of 5 to 6 carbon atoms free of aroma-tic unsaturation including alkyl su-bstituents of a total of no more than 4 additional carbon atoms, and X is a member selected from the class consisting ofv cyano, aminoet-hyl, and R NH group, and an R' A group, in which R is a member se leoted from the class consisting of a hydrogen atom,

an alkyl group of 1' to 18 carbon atoms, an alkenyl.

group or 3 to 18 carbon atoms, a phenylalkyl group of up to 18 carbon atoms, van alkylphenyl alkyl group of up to 30 carbon atoms, an alkoxyalkyl group of 3 to 24 carbon atoms, a hydroxyalkyl group of 2 to 12 carbon atoms, an alkylarninoalkyl group of 3 to 18 carbon atoms, R is a member selected from the class consisting of a hydrogen atom, an alkyl group of l to 12 carbon atoms, an alkenyl group of 3 to 12 carbon atoms, phenyl, naphthyl, a phenylalkyl group of up to '12 carbon atoms, an alkylphenylalkyl'group of up to 12 carbon atoms, an alkoxyalkyl group out 3 to 12 carbon atoms, a hydroxyalkyl group or up to 12 carbon atoms, and an alkylarninoalkyl group of 3 to 18 carbon atoms, and A is a chalcogen of an atomic weight of 16 to 32.

a 2. The compound having the formula R =NR oN V V in which R and R are alkyl groups of 1 to 18 carbon atoms, R R and R are ralkyl groups of 1 to carbon atoms, and R is a hydrogen atom.

3. The compound having the formula in which R and R are alkyl groups of 1 to 18 carbon atoms, R R and R are 'allsyl groups of 1 to 10 carbon atoms, and R is a hydrogen atom.

4. The compound having the formula 2 4 R 1 =NR R Nfi in which R and R are alkyl groups of 1 to 18 carbon atoms, R R and R are 'alkyl groups of 1 to 10 carbon atoms, and R and R represent hydrogen atoms.

5. The compound having the formula 2 4 R11 =N R in which R and R are :alkyl groups of 1 to 18 carbon atoms, R R and R are alkyl groups of 1 to 10 carbon atoms, R is a hydrogen atom, and R represents an alkyl group of 1 to 18 carbon atoms.

6. The compound having the formula R3 R 424 I R11 =NR Rm in which 'R and R are alkyl groups of 1 to 18. carbon atoms, R ,'-R and R are. alkyl groups of 1 to 10 carbon atoms, R and R represent hydrogen atoms, and Arepresents =a chalcogen of an atomic weight of 1 6 to 32.

7. The compound, having the formula in which :R and-R are alkyl groups of 1 to 18 carbon atoms, R R and R are alkyl groups of 1 to 10 carbon atoms, R is :a hydrogen atom, R is an alkyl group of 1 to 1-2 carbon atoms, and A represents a atomic weight of 16 to 32.

8. The compound, Z-cyano 1 (2-hydroxyethyl)-5-(2- hydroxyethylimino)-2,4,4-trimethy1pyrrolidine.

9. The compound, Z-cyano 5 dodecylimino-2,4,4-trimethylpyrnolidine.

10. The compound, Z-cyano 1 dodecyl-5-imino-2,4,4- trimethy-lpyrroltdine.

11. The compound, 2-am|inomethy=1 5 dodecylimino 2,4,4-trimethy1pyrro1idine.

12. The compound, S-benzylimino 2 hydroxy-2,4,4-. trimethylpyrrolidine. l v 1 3; A method tor the preparation ofthe compound ohalcogen of an .having the formula having the formula which comprises reacting T R4 R 1 =NR RGNH 1 which comprises reacting in substantially equimolecular proportions in the temperature range of about 0 to 70 C., the compound having the formula R NH with the compound having the formula Eton: \N/ =NR R5 in which the symbols R, R R R and R have the same significance as in claim 18, R is an alkyl group of 1 to 10 carbon atoms, R represents an alkyl group of 1 to 18 carbon atoms, and R is a member selected from the class consisting of an alkyl group of 1 to 9 carbon atoms and a hydrogen atom.

15. A method for the preparation of the compound R2 -R ml =NR 1w. f; which comprises reacting with R' AH in the temperature range of about 20 to about C., in which the symbols R, R R R and R have the same significance as in claim 19, R is an alkyl group of 1 to 10 carbon atoms, and R is a member selected from the class consisting of an alkyl group" of 1 to 9 carbon atoms anda hydrogenatom.

16. A method for the preparation of the compound having the formula temperature range of about I -19 in which R and R are each members selected from the class consisting of hydrogen, alkyl groups of 1 to 18 carbon atoms, phenyl, naphthyl, phenylalkyl groups of up to 18 carbon atoms, alkylpheny-l a-lkyl groups of upto 30 carbon atoms, al-koxyalkyl groups of 3 to 24 carbon atoms, hydroxyalkyl groups of 2 to 1-2 carbon atoms, andalkylaminoalkyl groups of 3 to 18 carbon atoms, R taken individually represents a member. selected from'the class consisting of alkyl, phenylalkyl, cycloalkyl, phenyl, napththyl, land alkylphenyl groups of no more than carbon atoms, R taken individually represents a member selected from the class consisting of hydrogen and alkyl groups of 1 to 4 carbon atoms, R and R taken individually represent members selected from the class consisting of hydrogen, .alkyl, cycloalkyl, phenylalkyl, phenyl, naphthyl, and

,alkylphenyl groups of up to 10 cambon atoms, R and R taken collectively with the carbon atoms to which they are joined form a carbocyclic ring of 5 to 6 carbon atoms tree of aromatic unsaturation including \alkyl substituents of a total of no more than 4 additionalcar-bon atoms, R and R taken collectively with the carbon atoms to which they are joined form a carbocyclic ring of 5 to 6 carbon atoms free of aromatic unsaturation including alkyl sub-stituents of a total of no more than 4 additional carbon atoms, R and R taken collectively with the carbon atoms to which they are joined form a carbocyclic ring of 5 to 6 carbon atoms tree of aromatic unsaturation including alkyl substituents of a total of no more than 4 additional carbon atoms, which comprises reacting a compound Whose principal tautomeric form is represented by the formula R V R4 1 R1 cumin with hydrogen in the temperature of 75 to 250 C. in the presence of a hydrogenation catalyst, in which R and R are each members selected from the class consisting of hydrogen, alkyl groups of 1 to 18 carbon atoms, phenyl, naphthyl, phenylalkyl groups of up to 18 carbon atoms, alkylphenyl-alkylgroups of up to 30 carbon atoms, alkoxyalkyl groups of 3 to 24 carbon atoms, hydroxyalkyl groups of 2 to 12 canbon atoms, and alkylaminoalkyl groups of 3 to 18 carbon atoms, R taken individually represents a member selected from the class consisting of alkyl, phenylalkyl, cycloalkyl, phenyl, naph-t-hyl, and alkyl-phenyl groups of no more than 10 carbon atoms, R taken individually represents a member selected from the class consisting of hydrogen and alkyl groups of '1 to 4 carbon atoms, R

and R taken individually represent members selected from the class consisting of hydrogen, alkyl, cycloalkyl, phenylalkyl, phenyl, naphthyl, and alkylphenyl groups of up to 10 carbon atoms, R and R taken collectively with the carbon atoms to which they are joined form a carbocyclic ring of 5 to 6 carbon atoms free of aromatic unsaturation including alkyl substituents of a total of no more than 4 additional carbon atoms, R and R taken collectively with the carbon atoms to which they are joined form a carbocyclic ring of 5 to 6 carbon atoms free of aromatic unsaturation including alkyl substituents of a total of no more than 4 additional carnbon atoms, and R and R taken collectively with the carbon atoms to which they are joined form a carbocyclic ring of 5' to 6 carbon atoms free of aromatic unsaturaiion including alkyl substituents of a total of no more than 4 additional carbon atoms.

18. A method for the preparation of the compound having the formula R2 a In; =NR RBN in which -R and R are each members selected from the class consisting of hydrogen, alkyl groups of 1 to 18 carbon atoms, phenyl, n-aphthyl, phenylalkyl groups of up to 18 carbon atoms, alkylphenylalkyl groups of up to 30 carbon atoms, allcoxyalkyl groups of 3 to 24 carbon atoms, hydroxyalkyl groups of 2 to 12 carbon atoms, and alkylaminoalkyl groups of 3 to 18 carbon atoms, R taken individually represents a member selected from the class consisting of alkyl, phenylalkyl, cycloalky-l, phenyl, naphthyl, and alkylphenyl groups of no more than 10 carbon atoms, R taken individually represents a member selected from the class consisting of hydrogen and alkyl groups of 1 to 4 carbon atoms, R and R taken individually represent members selected from the class consisting of hydrogen, alkyl, cycloalkyl, phenylalkyl, phenyl, naphthyl, and alkylphenyl groups of up to 10 carbon atoms, R and R taken collectively with the carbon atoms to which they are joined form a carbocyclic ring of 5 to 6 carbon atoms free of aromatic unsaturation including :alkyl substituents of, atotal of no more than 4 additional carbon atoms, R and R taken collectively with the carbon atoms to which they are joined form a carbocyclic ring of 5 to 6 carbon atoms tree of aromatic unsaturation including alkyl substituents of a total of no more than 4 additional carbon atoms, R and R taken collectively with the carbon atoms to which they are joined form a carbooyclic ring of 5 to 6 carbon atoms tree of aromatic unsaturation including alkyl substituents of a toal of no more than 4 additional carbon atoms, and R is a member selected fi'om the class consisting of a hydrogen atom, an alkyl group of 1 to 18 carbonatoms, an alkenyl goup of 3 to 18 carbon atoms, a phenylalkyl group of up to 18 canbon atoms, an alkylphenylalkyl group of up to 30 carbon atoms, on alkoxy- ,alkyl group of 3 to 24 carbon atoms, a hydroxyalkyl group of 2 to 12 carbon atoms, and an alkylaminoalkyl group of 3 to 18 carbon atoms.

19; A method for the preparation of a compound having the formula tau-tomeric tormhas the formula Bilg- 7 attached to no more than two other carbon atoms tr-cm the group R at a temperature of about 20 to about 75 C. and in which R and R are each members selected, from the class consisting of hydmogemalkyl groups of 1 to 18 carbon atoms, phenyl, naphthyl, phenylalkyl moups of up to 18 carbon atoms, alkylphenylalkyl groups of up to 30 carbon atoms, alkoxyalkyl groups of 3 to 24 carbon atoms, hydroxyalkyl groups of 2 to 12. carbon atoms, and allcylaminoalkyl groups of 3 to 18 carbon atoms, R taken individually represents a member selected from the class consisting of alkyl, phenylalkyl, cycloalkyl, phenyl, naphthyl, and alkylphenyl groups of no more than carbon atoms, R taken individually represents a member selected firom the class consisting of hydrogen and alkyl groups of 1 to 4 carbon atoms, R and R taken individually represent members selected the class consisting of hy- 22 drogen, alkyl, cycloalkyl, phenylalkyl, phenyl, naphthyl, and alkylphenyl groups of up to 10 carbon atoms, R and R taken collectively 'with the carbon atoms to which they are joined form acanbocyclic ring of 5 to 6 carbon atoms tree of aromatic unsaturation including alkyl substituents of a total of no more than 4 additional carbon atoms, R and R taken collectively with the carbon atoms to which they are joined form a carbocyclic ring of 5 to 6 carbon atoms free of aromatic unsaturation including alkyl substituents of a total of no more than 4 additional carbon atoms, R and R taken collectively with the carbonatoms to which they are joined form a carbocyclic ting of 5 to 6 carbon atoms free of aromatic unsaturati-on including alkyl substituents of a total of no more than 4 additional carbon atoms, R is a member selected from the class consisting of a hydrogen atom, an alkyl group of l to 12 car bon atoms, an alkenyl group of 3 to 12 carbon atoms,

phony-l, naphthyl, a phenylalkyl group of up to 12 carbon atoms, an alkylphenylalkyl group of up to 12 carbon atoms, an allcoxyalkyl group of 3 to 12 carbon atoms, a hydroxyalkyl group of up to 12 carbon atoms, and an .alkylaminoalkyl gnoup of 3 to 18 carbon atoms, and A is a chaloogen of an atomic weight of 16 to 32.

References Cited in the file of this patent UNITED STATES PATENTS 2,984,666 Bortnick May 16, 1961 

1. THE COMPOUND, A MEMBER SELECTED FROM THE CLASS CONSISTING OF THE COMPOUND HAVING THE FORMULA
 9. THE COMPOUND, 2-CYANO-5-DODECYLIMINO-2,4,4-TRIMETHLPYRROLIDINE. 